Thermoelectric power of mixed electronic-ionic conductors I. Basic equations

The present work considers thermopower of oxide materials within n-p transition regime. Specifically, basic equations describing the effect of thermocell reactions on both ionic and electronic component of thermoelectric power are derived. The proposed formalism considers the impact of gas/solid reactions on the relationship between thermopower and electrochemical potential within a system involving a metal oxide of nonstoichiometric composition and a metal (such as Pt) that is applied as a measuring electrode. The derived theoretical model allows the determination of the thermopower components corresponding to different charge carriers, including ions, electrons and electron holes, for metal oxides. The proposed model may be used for derivation of defect chemistry models based on thermopower data that are free of the ionic component.